DE2326793A1 - LIGHT SENSITIVE NON-SILVER SALT MATERIALS AND METHOD FOR MANUFACTURING PRINTING PLATE FROM THEM - Google Patents

Description

DR. E. WIEGAND DIPL-WG. W. NIEMANN DR. M. KÖHLER DIPL-ING. C. GERNHARDT

TELEPHONE: 555 476 8000 MONKS 2, TELEGRAMS: KARPATENT MATH I LD E N STRAS S E I2 '

V. 41652/73 - Eo / Ue May 25, 1973

Fuji Photo lilm Co., Ltd. Minami Ashigara-shi, Kanagawa (Japan)

Non-silver salt photosensitive materials and processes for the production of printing plates from them

The invention "relates to non-silver salt photosensitive materials, printing plates produced therefrom and a method for producing such Printing plates.

According to the invention are photosensitive materials with excellent storage properties that not based on a silver salt, indicated, which consists of a photosensitive layer

(1) a haloalkane, its bond dissociation energy is less than 75 Kcal / mole,

3 0:> j 5 1/1 Q S 3 '

(2) a furfurylidene acetal compound and

(3) optionally a phenolic compound to have.

The materials can be processed to form printing plates if the phenolic compound is present. Such plates and methods therefor are also given.

If furfural is heated under acidic conditions, a water-insoluble dark substance is formed, such as in "Handbuch der Organic Chemie", Beilstein, Volume 17 » Page 274 specified.

If furfural is reacted with a compound of the phenol type, a dark furfuro1 phenol resin is formed, as in "Encyclopedia of Polymer Science and Technology", Volume 7> Pages 432 to 445 indicated.

If, however, Furfurol is stored in a light barely becomes black gradually to image a resin and therefore it is difficult to photographic Manufacture materials using furfural.

Photosensitive materials taking advantage of the photosensitivity of lower ilalogehalkanes are known, and for example, haloalkane-aromatic amine type photographic media are disclosed in "Light-Sensitive Systems "described by J. Kosar, Chapter 8, or photographic Media from the low Ilalogenolkan-Furfuryliden Compound-primary aromatic amine -'lyp are disclosed in Japanese Patent 25952/71 and U.S. Patent 3,394,395 stated. Form according to the former Triphenylmethane dyes color images. According to the latter form Stenhouse dyes, which are the reaction product of aldehydes that are derived from furfurylidene compounds derive and are amines, color images.

3 U ,; 8 5 1/1 06 3

The aromatic amines listed above are easily oxidized. For example, when in air are left, they gradually blacken. That is why these aromatic amines are for practical use Unsuitable for use in photosensitive materials as they have these defects and often the background of the Discolor materials. .

An object of the invention is to provide light-sensitive materials of the non-silver salt type of excellent Suitability for storage.

Another object of the invention is photosensitive Non-silver salt type materials that colored latent images on exposure and colored visible images on heating.

Another object of the invention is in light-sensitive materials of the non-silver salt type which the formed latent image is converted into a visible image · within a wide "range of temperature can be.

Another object of the invention is new

em

Printing plates and a / method for making the printing plates.

In the context of the invention, numerous studies were carried out to avoid the disadvantages of those listed above common light-sensitive Nxcht bilber salt materials undertaken and found that preferred furfural resins or furfural phenolic resins as image-forming Component are used and the furfural phenolic resins are used for printing plate production »

The above objects of the invention are obtained when a photosensitive layer, which is a photosensitive ealogenalkane, preferably

3 ü- ^ S 1/1 0 6 3

_ Zj. -

2326733

of the following formula (I), having a bond dissociation energy less than 75 Kcal / mole is used. Preferred materials are the following furfurylidene aetal compounds of the following formulas (Ha) or (lib):

- R-CX ₃ '(I)

wherein X is a halogen atom, where each other, the radicals X from each other can distinguish or a hydrogen atom without however, all X radicals are hydrogen atoms, means and R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 7 carbon atoms, a halogen-substituted alkyl group having 1 to 7 carbon atoms, a Acyl group or an acyl group substituted with a halogen atom or one substituted with a halogen atom Represents arylsulfonyl group, a nitro group or an aryl group. For the formation of photosensitive materials as such, however, it is preferred that R be a hydrogen atom, a halogen atom, or a halogen-substituted one Represents an alkyl group having 1 to J carbon atoms;

O - R ₁

'■ (Ha)

3 0 9 8 5 1/10 8 3

wherein E. and Eo one or two phenyl groups or one or two aralkyl groups having 6 to 9 carbon atoms, where the phenyl or aryl ring in the aralkyl group having a halogen atom or an alkoxy group having 1 to 3 carbon atoms may be substituted, or one or two furfuryl groups; ·

CL

R ^ (Hb)

wherein Ev is an alkylene group with 2 to 7 carbon atoms, which can be substituted by a hydroxyalkyl group with 1 to M carbon atoms or an imino group, or can be dimerized via a spiro carbon atom, as in the formula I c, if E is the group H or CH- indicates represented. Preferred groups E-, in both embodiments are those in which E-, a methylene chain with 2 to 3 carbon atoms, which can be substituted by an alkyl group with 1 to 4 carbon atoms, a hydroxyalkyl group with 1 to 4 carbon atoms or an imino group and which can be substituted by a Spiro carbon atom can be dimerized in the manner described above, means.

The photosensitive layer according to the invention preferably contains in addition to the above light

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sensitive haloalkane of the above formula (I) and the furfurylidene acetal compounds of the above formulas (Ha) or (Hb) a compound of the phenol type of the following formulas (HIa) or (HIb):

(OH)

(HIa)

(OH) _n (HIb)

wherein η is an integer from 1 to J and E ^ a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having Λ to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 bi ^; s 12 carbon atoms, a formyl group, a sulfo group (S0-wH <} - j an amino group or an aeyl group. with. Ibis Φ carbon atoms. The

3ÜS8 5 1 / t 0 6 3

Amino group is used for the 3Hcht sirber salt photosensitive materials not preferred as such.

The printing plates are made by imagewise exposure to a Element comprising a photosensitive layer made from the photosensitive haloalkane, the furfurylidene acetal compound and a phenol compound given above has, to Lieht, uniform heating of the photosensitive layer and treating the photosensitive layer with a solvent.

The replacement of the group 'R ₁ in the phenolic compound has a great influence in that it increases the oleophilic properties of the image parts of the printing plate *

The general by the foregoing; ' Formula (I) reproduced Haloalkanes set free a halogen radical and this Ka.dikal takes a hydrogen a.tom from the Solvents or similar materials and forms a hydrohalic acid. Therefore there is a large amount of acid on the imagewise exposed part as a latent image. On the other hand, the furfurylid «· compound activated in the presence of the acid formed in this way, which acts as a catalyst, and is transformed into an image-like furfural resin of black or dark shade convicted.

The haloalkanes used in this embodiment of the invention include compounds whose bin * - dung dissociation energy (energy to form-ties first free ealogen radical) is less than 75 koal / col, preferably those whose binding dissociation energy is less than 70 Kcal / mole. These are in "Light-Sensitive Systems "given by J. Kosar * Examples for this are! Eetrabromocarbon :, Iodoform,

106.3

carbon, hexachloroethane, 1,2-Dijοdathan, Bromtri-J ο da than, bromodio'odethane, triiodoethane, triiodopropane, Hexabromohexane, hexajodhexane, hexabromoheptane, α, α, α-tribromoacetophenone, α, α, α-trichloroacetophenone, α, α, α-p-tetrabromoacetophenone, α, α, a-Tribomethylphenylsulfon, α, α, a-tribromomethyl-p-tolylsulfone, a, a, a-tribromo-p-nitroacetophenone and α, α, α-dibromo-p-methylacetophenone and similar materials. In addition, halogen-containing Compounds that form halogen radicals on exposure to light or the halogen acids in the presence of phenol compounds are used.

In the non-silver salt photosensitive materials as such ", the following compounds are preferred: carbon tetrabromide, carbon iodoform, carbon tetraiodide, hexachloroethane, hexafluorathane, 1,2-di $ ο dathane, bromotriiodomethane, chlorodijodmethane and the like, which are solid at room temperature, and especially become Carbon tetrabromide and iodoform are preferred.

The furfurylidene compounds used in the context of the invention can be easily produced by reacting furfural and an alcohol.

For example, difurfurylidene pentaerythritol can through Heat 1 mole equivalent of pentaerythritol and 2 mole equivalents Furfural in toluene in the presence of a catalytic amount of p-toluenesulfonic acid, for example 1/1000 mole equivalent to the reactants, removing 2 mole equivalents of water from the azeotrope Mixing by means of a quantitative water receiver (Distilling Tube Receiver 0 411 Shibata Kagaku Kikai Kogyo) and pouring the reaction mixture into a large amount of water to precipitate the product will. All connections from the furfurylid

309 8 51/106 3

acetal type among the FurfuryIiden compounds can after the introductory procedure only by changing the Starting materials are produced:

CHO -K-2R0H ~ - * kL J-CHI '+ H ₉ O

For example, the compound 1 given below can be prepared in the following manner: 2 moles of furfural (192 g), 1 mole of pentaerythritol (136 g) and 0.2 g of p-soluenesulfonic acid were placed in a 2 liter flask fitted with a still tube receiver and with a cooling tube was equipped, heated to reflux and used 1 liter of benzene as the solvent. When the reaction progressed, water appeared in the above recording device and the reaction mixture turned black and some precipitation occurred. After the water was fractionally distilled off, it became the reaction product filtered and poured the Ultrat in 3 1 ligroin, whereupon flaky crystals appeared. 200 g of yellow crystals (melting point 161 to 16 ° C) of compound 1 obtained.

The following are examples of furfurylidene compounds , which can be used according to the invention, given:

3 09851/1083

0 - CH ₂ OH ₂ -

0 -

-O

(Dimerization by a spiro carbon atom)

Difurfuylidene pentaerytiirite

.

™ ^CH

0 - C _x

\ X

^X 0 - CH ₂ ^

C ₂ H

3? Urfur'yliden-2-ethyl-2-hydroxymethyl-1,3-propylene ether.

-CH

- CH,

TLl

Purfuryli dendi f urfuryläther "

3 0 9 8 5 1/10 6 3 '

^X O-CH ₂ "N = CH

K. J

i ¹ urfuiyliden-2-methyl-2-furfurylidenimino-1,3-propylene ether.

5.

-CH

0 - C

CH-

¹ CH-

0 - C

/ ^GH 3

! "urfuryli dentetrame ethyl ethyl ether.

6th

. 0

CH

p - CH ₂ CH ₂

- CH ₂ CH ₂

Furfurylidene diphenethyl ether.

Ü 9 β 5 1/1 0 6 3

O - CH,

• O

O - CH,

Furfurylidene dibenzyl ether.

O - CH,

«K J- *

OCH-

0 - CH,

CH-

Purfurylidenedianisylather.

0-CH

O - CH,

rs

I ¹ Ur fury Ii dendib en zhy dry lather.

309851/1063

10.

.0.-CH,
-CH,

-CH ₂ - / Vc-3

Furfuiylidene bis (p-chlorobenzyl) ether _e

The light-sensitive non-silver salt materials according to the invention preferably consist of one
Support and the photosensitive layer applied to this support and contain the components listed above. The photosensitive layer may further contain a film-forming binder. In many cases, the layer preferably contains one
Binder, especially to form a printing plate «. Any of the known binders can be used as the binder, for example nitrocellulose, benzyl cellulose, polycarbonate, polyvinyl acetate, cellulose acetate, cellulose acetate butyrate, cellulose acetate phthalate, polyvinyl chloride, polystyrene, polyester, polymethyl methacrylate, polyvinyl pyrrolidone, polyvinyl butyral, it should be noted that it is polyphenylene oxide Heating area
for fixation depending on the choice of tie
and the combinations thereof may vary. The binders used in the embodiment for printing plates

309851/1063

are preferably resistant to temperatures less than " 200 ° C and do not react with the compounds in the layer.

Vie "already indicated above, the tasks of the present invention can be obtained even more advantageously when a phenol type compound of the formulas (HIa) or (HIb) is incorporated in the above photosensitive layer.

Illustrative examples of compounds of the phenol type are, for example, pyrogallol, methyl gallate, ethyl gallate, n-propyl gallate, isosmyl gallate, lauryl gallate, stearyl gallate, bile acid, phloroglucinol, 2,4,6-trihydroxytoluene, 2,4,6-trihydroxyacetophenone, J-trihydroxyacetophenone ->^;'-' ^:! Catechol, 3,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxy-3j5-di-tert-butybenzoic acid, 2,6-dihydroxybenzaldehyde, 4,5-dicydroxytoluene, resorcinol, 4-chlororesorcinol , 3,5-dihydroxytoluene, hydroquinone, p-hydroxybenzenesulfonic acid, ρ-bromophenol, 1,5-l ⁾ iliydroxynaphthalene, 1,2-dihydroxynaplithalin, 1,3-dihydroxynaphthalene, 2,7- ^ ihydroxynaphthalin-3-sulfonic acid and the like. 2,4-Dihydroxy-5-bromobenzoic acid can also be used, but is not preferred as such for light-sensitive IT non-silver materials »

Due to the use of the phenol type compound, it becomes possible to extremely increase the image density, which is sometimes somewhat inadequate in the layer containing a haloalkane and an ITurfuryl den compound. The effect of the phenol type compound becomes higher as the hydroxyl groups contained therein increase. from From this point of view, the phloroglucinol derivative becomes special preferred «= Another advantage of using the compound of the phenol type is that the latent

30385 1/106

Image colored in a yellow, orange or pink ϊοη depends on the structure of the layer. That's why it is possible to convert the latent image into a colored one and therefore they are the link between the Phenol type-containing photographic materials "for forming various kinds of desired images to preferred ·.

The action of the phenol-type compound is believed to be as follows: It is believed that the halogen sulfide and the phenolic compound form a dye benzene type through a dehydrohalogenation reaction according to the following reaction formula form:

Lies

+ 4HBr

i ^m hx

If a photosensitive material, which one Dispersion of a haloalkane and a polyphenylene uniformly dispersed in a binder, exposed to light exposed will actually have the same staining established. However, when the obtained dye is heated the material will only yellow and fade without blackening it. With regard to this Br-

3 0 9 8 5 1/10 6 3

2328793

Visions are believed to be the dye itself does not have any significant influence in the photosensitive System according to the invention has. Venn continues a furfurylidene compound to the above is applied, in which a benzene type dye is formed, and then heated is, only the part where the dye is formed is blackened in the dark. I. E. it is this assume: A large amount of acids are formed in the part of the latent image and thereby the furfurylidene compounds in. . Furfural

converted due to the catalytic action of the acid and then the! furfurol begins

to react with the phenolic compound to form a furfural-phenolic resin. The mechanism the formation of the furfural-phenol resin is as follows, including on "Kunststoffe", by Koschulz, Volume 23 (1933), page Reference is made: In the first place, a precondensation reaction takes place between the furfural and the phenolic bonds according to the following Eeaktionsschema and the obtained precondensation product is under Heat in a dark resin or furfural-phenolic resin with its own three-dimensional network structure Inclusion polymerization of the furan ring transferred;

CHO

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In the sensitive materials according to the Invention, the materials listed above, namely lower halo-alkane, furfuryl! Denacetal compound and phenol compound, the lower haloalkane reacts with the phenol compound in the Exposure to liberation of hydrogen halide and the hydrogen halide obtained acts to hydrolyze of the furfurylidene acetal compound in furfural «Then the furfural formed in this way reacts with the phenolic compound to form

of a precondensation product <> The pre-condensation product obtained is then converted into a resin with a ternary or three-dimensional structure by heating =. In this respect, it should be noted that the compound of the phenol type added to this system is used as a sensitizer and acts as a coloring agent =

The photosensitive materials according to the invention are obtained by dissolving a haloalkane _? a FurfuryIidenacetal compound and optionally a film-forming binder and further optionally a compound of the phenol type, the latter two components being used for the purpose of a printing plate, in an organic solvent, for example toluene, benzene, dioxane, alcohol, tetrahydrofuran, chloroform, methyl ethyl ketone, ethyl acetate or the like, and subsequent application of the solution obtained on a carrier.

To achieve the best results, the haloalkane with a dissociation energy of less than 75 Kcal / Hol, preferably less than 70 Kcal / mole, in an amount from about 0.01 to about 100 grams per square meter of support

3ÜJÖ5 1/1063

In general, it is up to the execution form for

Printing plates preferably in an amount of 0.5 to 10 g / m 2 of the support, while in the embodiment of a light-sensitive non-silver salt material, the use of somewhat smaller amounts is justifiable, i. E. where it is only desired to form an image, and in this case the preferred amount of the haloalkane is 0.2-0.5 g / m · These ranges may of course overlap, but generally smaller amounts are used for image formation as such and somewhat larger amounts Quantities are used to form printing plates? where the layer removal is imperative. To achieve the best results, the following parts by weight of the components are used for 1 part by weight of the haloalkane: furfurylidene acetal about 0.05 to about 50, preferably 0.1 to 105 phenol compound about 0.05 to about 100, preferably 0.1 to 20 and Jilmbinder about 0.03 to about 10, preferably 0.1 to 5. Such systems are easily applied from a solvent in an amount of about 10 to about 50 O _3, preferably 50 to 500 on the same basis. The above ranges find the most favorable application in the embodiment for printing plates.

In the embodiment for light-sensitive silver salt light-sensitive materials However, the Gexd aspect ratio from haloalkane to uurfuryl compound preferably 0.1 to 35, more preferably 0.5 to 2, and the weight ratio of the phenol type compound to the furfurylidene compound is preferably 5 or less, more preferably 0.05 to 2 »the amount of the binder to be used is not particularly limited and it is sufficient if he carries the respective components «A preferred

3 0 .1 B 5 1/1 0 6 3

Weight ratio of haloalkane to binder is J within the range of from about 0.03 "to about 10, preferably from 0 ₅ 1" to 5 parts by weight of the halogen-alkane to parts by weight of the binder "

Any carrier commonly used in the art can be used as the carrier. "for example papers, plastic films or metal plates, like aluminum plates or the like ο with regard to the Paper carrier is baryta paper or one with a high molecular compound, such as polyethylene, polyvinyl alcohol, coated paper is particularly preferred.

The strength of the drawn film for the light-sensitive Layer is generally 0.1 to 50 microns, more preferably 1 to 1.0 microns for the Kicht silver salt embodiment = Excellent results are obtained in the embodiment for printing plates, if the thickness of the photosensitive layer is about 0.1 to about 30 microns, more preferably 0.5 "to 10 microns»

To form printing plates, however, the surface of the carrier must be hydrophilic so that it can be used as a Pressure plate works, if the selected carrier is not of is hydrophilic, the surface of the support can be treated by known methods, such as chemical treatment, Grain, anodizing, application of a hydrophilic layer then and the like = to be made hydrophilic =

There are no significant limitations with regard to the carrier, unless it applies to the ones applied Excessive heating conditions or by the solvent used is damaged = the degree of hydrophilicity exhibited by the carrier is not particularly high important insofar as it is generally within the ranges of the hydrophilicity hitherto applied to the printing plates.

/ 1083

When an image is formed using the photosensitive material according to the invention, the material is exposed imagewise to light having a wavelength of 300 to 6000 α and then heated to a temperature in the range of room temperature to 200 ° G. The preferred heating conditions are within a range of about 50 "to about I5O ⁰ C for about 3O seconds to 5 minutes. The heating xvird for the purpose of resin formation, ie Eeaktionsbeschleunigung executed and for the removal of the remaining haloalkanes, ie fixation, so that the The period of time for the heating can be freely determined. In certain cases, the heating stage can even be omitted and a permanent image can be formed.

In the Ausführungεform of the printing plates, the photosensitive material is image according to the invention * v ^r else to light having a wavelength of about 3ooo exposed to preferably 5OOO S. Electromagnetic waves whose

• Wavelength less than 3OOO A can also uses \ tferden. The exposure can be by means of a mercury lamp or the like, for example one Xenon lamp and the like., Are performed. The exposed material is then uniform to a temperature of Heated room temperature to about 200 ° C. In general, the heating takes place for a few seconds to 20 minutes, usually heating for 30 seconds to 5 minutes at 100 ° C or in this area to obtain superior printing plates «Heating can also be done with an infrared radiation of 2» 5 up to 20 microns «,

In the version for printing plates, the distinguishable images then with a solvent

309851/1063

Removal of the unnecessary parts in the printing plate, ie. the non-printing parts or unexposed parts, treated so that the hydrophilic surface of the support is exposed. The solvent used can be appropriately selected based on the binder used. Usable solvents include, for example, alcohols, preferably Qy, - to CQ-alcohol, such as methanol, ethanol, propanol, butanol, cyclohexyl alcohol and ethylene glycol, ketones, preferably Gy, - to Cg-ketones, such as acetone, methylethyl ketone and cyclohexanone, aromatic solvents, preferably Cr to C ^ q aromatics, such as benzene, toluene and xylene, ethers, preferably C2 to Cg ethers, such as diethyl ether, dioxane and tetrahydrofuran, and esters, preferably C ^ to C ^ esters, such as ethyl acetate ^ Ethyl formate and γ-butyrolactone.

Generally good results will be obtained with the. following treatment conditions obtained with solvents: Temperature atm about ⁷ Jd to about 200 ° C, preferably 50 I5O ^{0 c} "Time about 2 to 3 seconds to about 10 minutes, preferably 30 seconds to 5 minutes, pressure 1, although lower or superatmospheric pressure can be applied.

According to the invention, there are good printing plates with excellent printing resistance by exposure to Receive light, heating and solvent treatment. Since there are still visible images during manufacture of the printing plates, an assessment of the printing plate can be easily carried out.

According to the invention, the furfurylidene compound used is very stable, so that the photosensitive materials obtained have excellent storage properties own for a long period of time

30a851 / 1063

and further, an image with low background feature leckung be formed. Further, a permanent image can be obtained in numerous cases only by an operation associated with the heating step, and the obtained image has excellent properties such as high weather resistance, high chemical resistance and the like, that is, no leaching or fading occurs in the image . In this respect, the photosensitive materials according to the invention have various advantages which cannot be obtained from the conventional photosensitive materials for forming colored images.

The invention is further illustrated below with the aid of the following examples, in which Examples 1 to 5 deal with non-silver salt photosensitive materials as such and Examples 6 to 15 deal with the execution ε form for printing plates.

In the examples, all percentages are by weight unless otherwise specified.

example 1

After 0.1 g of difurfurylidene pentaerythrite and 0.1 g Iodoform in 3 g of a 5% polystyrene-benzene solution (Polystyrene having an average degree of polymerization of about 900) was dissolved, the obtained was Solution applied to a photographic baryta paper using a coating stick and then during 30 minutes in a drying chamber at 70 ° G for production of a photosensitive material with a photosensitive layer thickness of about 3 microns.

309851/1063

The photosensitive material thus prepared was contacted with a negative film and for 20 seconds by means of a diazo-type multiplier with a built-in 600 W mercury vapor lamp exposed at a distance of 20 cm, whereby a yellow image was obtained (main wavelength 3 ^ 50 S).

Then the material was heated to 120 ° C. for 120 seconds and a brown image with an eef lection density of 1.35 obtained «The background of the material was colorless. If the material is exposed to sunlight during was suspended one day, the background turned yellow while the image remained unchanged «.

Example 2

0.1 g Difurfurylidenpentaerythrit, O ₅ I _r g tetrabromo carbon and 0.1 g of phloroglucinol were dissolved in 3 S a 3?% Polystyrene-tetrahydrofuran solution (polystyrene having an average degree of about 900), and the obtained solution onto a photographic baryta applied using a mounting stick and then dried for 15 minutes in a drying chamber at 50 ° C to a light-sensitive layer thickness of about 3 microns »

The light-sensitive paper was closely contacted with a negative film and vapor lamp for 20 seconds by means of a diazo-Yervielfältiger with built ¥ 600 -Quecksilber ^ 20 cm of the element exposed to 9 ifodurch a positive _s with strong dark green colored image was obtained "The Reflektionsdiclite of formed image was 1.41 »

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The paper then rose for 30 seconds 110 ° C, causing the color of the picture to change Black changed and its reflection density increased 1.86 was increased. There was no discoloration of the background of the paper.

If the material has been left in a bright room without exposure to direct sunlight, the color did not change and the background was not discolored.

If the material was continuously exposed to direct sunlight for 1 week, it would become so Color image not changed, while the background looked a little pale brown in color.

In addition, it was prepared in the above manner light-sensitive paper using the Uniarc 250-60 device (manufacturer: Ushio ElectrieJCo., Main wavelength 3650 S) with a built-in 250 W super high pressure mercury vapor lamp (Light source for IC printing) at a distance of 40 cm from the shutter exposed and then heated to 110 ° C with a hot plate. The color density of the image obtained is given by following table:

Exposure time -

(Seconds) 100 50 25 12.5

Deduction time

(Seconds) 10 10 10 10

Optical density O ₉ 99 O ₉ 75 0.61 O ₅ 33

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Example 3

0.1 g difurfurylidene pentaerythritol, 0.1 g iodoform, 0j1 S pyrogallol and 3 S of a 10% polyvinyl butyraltrahydrofuran solution (Polyvinyl butyral: average degree of polymerization about 700) were used to produce a photosensitive paper with a photosensitive A layer thickness of 3 microns was drawn up and the treated paper was exposed as in Example 2, with an image with orange color was formed on a background of pale yellow color. The received paper was then heated to 100 ° G for 30 seconds, whereby the color of the image changes to a dark black-brown Color changed.

Separately therefrom was a photosensitive paper prepared in the above manner, wherein However, only 0.1 g of iodoform and 0.1 g of pyrogallol were used, exposed to light. Venn that too Orange color image was obtained, the color of the obtained image faded to a pale yellow color after heating under the same conditions as above.

Example 4

0.1 g of furfurylidene acetal, 0.1 g of a haloalkane and 0.1 g of a phenol type compound were dissolved in a 10% resin solution as shown in the following table. The resulting solution was applied to a baryta-coated paper and dried, and a photosensitive layer of 4 µl thickness as in Example 2 was obtained. The one made in this way

309851/106

photosensitive material was exposed and heated as in Example 2.

I \ irfury Ii den connection

Difurfurylidene pentaerythritol

as well
as well

as well

as well

3Purfüryli den-2-ethyl-2- Hydroixymethyl 1,3-propylene ether

Purfuryli denfurfuryl- alcohol

Purfuryli den-2-methyl-2-furfuryli denimino-1,3-propylenea the r

IOr furyli dendipheny lather

Haloalkane compound of phenol

High molecular weight binder (resin)

colour

Carbon tetrabromide

likewise likewise

Iodoform

as well

as well

as well

likewise bile acid polystyrene * brown

n-ethyl gallate

1,5-dihydro3cy-

naphtha lin

2,4,6-dihydroxyacetophenone

2,4,6-di

hydroxy

toluene

Phloroglucine

Phloroglucine

Phloroglucine

likewise likewise

Polyvinyl butyral "*

as well

likewise likewise

Olive brown

yellowish brown

dark green

dark green

Polystyrene * dark green

as well as pyrogallol as well

black

dark green

Brown

* Average degree of polymerisation approx. 900 ** Average degree of polymerisation approx. 700

3 09851/1063

Example 3

0.1 g of difurfurylidene pentaerythritol, 0.1 g of carbon tetrabromide and 0.1 g of a compound from Eh. ene type of oil in a ^% lgen polystyrene tetrahydrofuran as achieved in Example 2 and treated as in Example 2, to obtain the liciitempfindliche material "The material was at Lieht during J> 0 seconds using a 600 W-diazo-duplicator Exposed 20 cm of the material (major wavelength $ 365O -) and a visible latent image that was colored pale brown was formed. After exposure to 110 ° C. for 60 seconds, a brown image with a reflection density of 0.5 to 0.9 was obtained. The phenol-type compounds added to the photosensitive materials to form a number of different elements were as follows: methyl gallate, propyl gallate, isoamyl gallate, _s lauryl gallate,

Tbrenz Brenz

3-Metlio2y} £ J atechin, fSatechin, 2,5-dihydroxybenzoic acid, 5,4-Uihydroxybenzoesäure, 2,4-dihydroxy-5-bi ^'i ombenzoesäure, 2,6-Bil3ydro: xybenzaldehyd or p-hydroxybenzenesulfonic acid.

Example 6

A material for producing a printing plate was dureJi resolution of 0.1 g of carbon tetrachloride, 0 ₂ 1 g Difurfurylidenpentaerythrit and O ₅ I g phloroglucinol 3 S a 5% ig ^en tetrahydrofuran solution of polyvinyl butyral (Esles BM 5 _S Sekisui Kagaku) and on transfer of the The resulting liösoag produced on an anodized aluminum plate "- The thickness of the photosensitive layer was 2 microns" The modifying conditions were; 40 % phosphoric acid,

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. - 28 -

2326733

Barely any temperature, 10 A / cm current for 2 minutes. This is a common practice.

A negative film was brought into physical contact with the obtained plate-making material. That Printing plate making material was then exposed to light from a 600 W mercury lamp at a distance of 20 cm Pylex-illter exposed for 20 seconds, whereupon a positive print image was formed.

This printing plate production material was then heated on a hot plate to 110 ° C. for 1 minute, whereupon the positive print image changed to a dark brown color image. By washing with methanol at tree temperature during Λ minute the unexposed portions have been removed, that is peeled off. Further washing with water gave a printing plate for the negative procedure, the exposed parts retaining the brown image.

Although this printing plate could be used on a printing machine as it was, it was possible to use the To increase the oleophilic properties of the image part and to improve the abrasion resistance by applying a varnish this was then applied »Furthermore, the hydrophilic properties of the Mcht image part were subjected to a rubbing treatment improved.

Example 7

A printing plate making material was prepared by dissolving 0.1 g of carbon tetrabromide, 0.2 g of difurfurylidene pentaerythritol and 0 _sec 6 g of phloroglucinol in 9 S of a fig tetrahydrofuran solution of polyvinyl butyral (Esles BM 5 s Sekisui Kagaku) and applying the resulting solution

30 9851 / 1-0.6: 3:

an anodized aluminum plate is made. The strenght the photosensitive layer ranged from 1 to 4 microns. -

Then a positive film on the obtained printing plate making material In the same manner as in Example 6, it was exposed to light and treated by heating at 110 C for 2 minutes. A deep dark green image appeared on the surface of the printing plate making material.

The printing plate material was then treated with ethyl alcohol at room temperature for 2 minutes and then with water see gexva at room temperature for 2 minutes. One Printing plate for the positive way of working x-rarde included obtain.

Furthermore, the printing plate was coated with a printing ink for improving the oleophilic properties of the image parts treated to form a positive image. If the plate has been rubbed, were the hydrophilic properties of the ificht image parts further improved.

Example 8

, A printing plate-making material vrarde by dissolution of 0.1 g of carbon tetrabromide, 0.1 g of difurfurylidene pentaerythritol and 0.1 g of 4-ethylresorcinol in 3 g of a 5% strength tetrahydrofuran solution of polymethyl methacrylate and applying the obtained solution to the same support and in the same manner as in Example 6. The thickness of the photosensitive layer ranged from 1 to 4 microns.

A printing plate for positive work was made

30985 1/1063

by. Exposure to light in the same way as in Example 7 produced, where "the heat treatment (110 ° C.) was carried out for JO seconds and then was treated in the same manner as in Example 7.

Example 9

Printing plate making materials have been made by. resolution of 0.1 g of carbon tetrabromide, 0.1 g of one of the following furfurylidene acetal compounds, and 0.1 g of one of the following phenolic compounds in a 5% tetrahydro furan solution of polyvinyl alcohol (Sebian A-235, Daisel Co., Ltd.) and applying the obtained solutions to the same support and in the same manner as in Example 1 produced. The thickness of the photosensitive layer ranged from 1 to 4 microns in each case.

Positive printing plates for positive work were made by exposure to light in the same way as in Example 7 »Execution of the heat treatment at 110 ° C during the period indicated in the table below and subsequent removal of the unexposed Parts made with a solvent (plate making treatment):

309851/1063

_r - 31 -

2326733

Phenol compound

Brenzkr-techin Catechol

Pyrogallol hydroclinone

Furfurylidene acetal compound

Difurfurylidene pentaerythritol

Furfurylidene-2-methyl-2-furfurylideneimino-1,3-propylene ether

Di furfuryl! Den-penta erythritol Difurfurylidene pentaerythritol

4-bromoresorcinol difurfurylidene pentaerythritol

4,6-dichloro-difurfurylidene-pentaerythritol resorcinol

5-methyl difurfurylidene pentaerythritol

resorcinol

5-llethyl xe sorein

2-methylresorcinol

Eesorcinol resorcinol

2-aminopiienol

Λ , 3-Di-

liydroxynaphthalene

4-methoxy-naphthol

2,4,6-tri-

j-2- ethyl-2-hydroxy methyl-1,3-propylene ether

Di furfuryIi den-Pen ta e rythri t

Difurfurylidene pentaerythritol

Furfuryl! Den-bis- (p-chloro- ■ benzyl ether)

Difurfurylidene pentaerythritol difurfurylidene pentaerythritol

Di furfuryl! den-Penta ery th-ri t Di furfuryl! Den-penta erythritol

y
toluene

2,4,6-tri-

liydroxyaeetophenon

Furfuryl den-dianisyl ether

Heating period (seconds)

120

120 60 120

60 40

60 180

■ 60

0985 1/1063

Example 10

A printing plate making material was made by Dissolution of 0.1 g carbon tetrabromide, 0.1 g difurfurylidene pentaerythritol and 0.3 g of phloroglucinol in 4 g of a 5% ethyl acetate solution of cellulose acetate butyrate and applying the obtained solution to an anodized aluminum plate in the same manner as in Example 6 manufactured. The thickness of the photosensitive layer ranged from 1 to 4 · hikron.

The printing plate making material was exposed to light in the same manner as in Example 7, heated to 110 ° C and treated with a solution of ethyl alcohol / acetone (2: 1 by volume) of 2 ^ ° G for 3 minutes and then washed with water at 25 ° C for 30 minutes. The plate was then treated by the same plate-making treatment as in Example 6,., Whereby a printing plate for positive work was obtained,

Example 11

A printing plate making material was prepared by dissolving 0.1 g of carbon tetrabromide, 0.1 g of difurfurylidene pentaeythritol and 0.1 g of phloroglucine in a 5% Tetrahydro furan solution of polyvinyl formal (Denka i'ormal 3000, Denki Kagaku Kogyo Co., Ltd.) with application of the obtained solution on an anodized aluminum plate in prepared in the same manner as in Example 6. This printing plate making material was exposed to light in the exposed in the same way as in Example 7, to 60 ° C heated for 5 minutes, once with ethyl alcohol

3098 5 1/106 3 "

of 40 ° C for 2 minutes and then washed with water of 25 ° C for 1 minute, thereby making a printing plate was received for positive work. The thickness of the photosensitive layer ranged from 1 to 4 microns.

Example 12

A printing plate making material was prepared by dissolving 0.1 g of iodoform, 0.1 g of difurfurylidene pentaerythritol and 0.3 g of phloroglucinol in a 5% tetrahydro for dissolving polyvinyl acetate and applying the contained solution on an anodized aluminum plate prepared in the same manner as in Example 6. The thickness of the photosensitive layer was in the range of 1 to 4 microns.

The positive work printing plate was made by suspension of light, heating and washing in the same manner as in Example 7.

Example 15

A printing plate making material was prepared by dissolving 0.1 g of carbon tetrabromide, 0.1 g of 2,5-dihydroxybenzoic acid and 0.1 g of difurfurylidene pentaerythritol in a 5% tetrahydrofuran solution of polyvinyl butyral as in Example 6 and applying the resulting solution to an anodized aluminum plate in the same manner prepared as in Example 6. A negative work printing plate was made by exposure to light in the same way as in example 6, application of heat by means of a 500 watt infrared lamp at a distance of 15 cm

30 9851/1063

for 4 minutes and then carrying out the Plate-making treatment in the same manner as in Example 6 was prepared. The strength of the photosensitive Layer ranged from 1 "to 4 microns.

Example 14-

A printing plate making material was made using of 0.1 g of α, α, α-p-tetrabromoacetophenone, 0.1 g of difurfurylidene pentaerythritol and 0.1 g of phloroglucinol prepared in the same manner as in Example 6. This Printing plate making material was exposed to light and heated in the same manner as in Example 6 and Treated with a solvent "and get a printing plate for positive work. The strength of the photosensitive Layer ranged from 1 to 4 microns.

Example 13

A printing plate making material was prepared by dissolving 0.2 g of α, α, α-tetrabromoacetophenone, 0.1 g Difurfurylidene pentaerythritol and 0.06 g phloroglucinol in a 5% tetrahydrofuran solution of polyvinyl butyral. as in Example 6, application of the solution obtained to an aluminum plate, the surface of which was grained, and Drying made. The thickness of the photosensitive layer ranged from 1 to 4 microns. This printing plate material was exposed, heated and treated with solvent in the same manner as in Example 6 and get a printing plate for negative work.

3 0 9 6 5 1/10 6 3

Example 16

A printing plate making material was prepared by dissolving 0.1 g of α, α, α-iribromomethylphenylsulfon, 0.1 g of ITurfurylidene-2-ethyl-2-hydroxymethyl-1,3-propylene ether and 0.1 g of phloroglucinol in a tetrahydrofuran solution of polyvinyl butyral and subsequent treatment in the same manner as in Example 6. The thickness of the photosensitive layer ranged from 1 to 4 microns = The printing plate making material was exposed to light, heated and treated with a solvent, and a printing plate for positive work was obtained =

From the foregoing, it can be seen that the haloalkane and the phenol compound are related to each other react during exposure and a large amount of hydrogen halide is formed = the one formed in the process Hydrogen halide is used as a catalyst, for example single-opening poly .ierisation of the 5 "urfurylidens, and the acidic polycondensation of the phenolic compound and of the hydrolysis product of the furfurylidene compound and the like expires. Uniform heating shortens the reaction time in the above implementation *

In the foregoing, the invention has been described on the basis of preferred embodiments, without being subordinate to this is limited.

309851/1083

Claims (16)

Claims Non-silver salt photosensitive materials, containing a photosensitive layer comprising a photosensitive haloalkane having a dissociation energy of less than 75 Kcal / hol and a! "urfurylidenacetal compound of the following formula contains (Ha) or (Hb): 0 - R-, (Ha) wherein R ^ and Ro are one or two phenyl groups or one or two aralkyl groups having 6 to 9 carbon atoms, where the phenyl or aryl ring in the aralkyl group having a halogen atom or an alkoxy group having 1 to 3 carbon atoms may be substituted, or one or two i \ irfurylgruppen; (Hb). 309851/1063 2326783 wherein E-, an alkylene group with 2 "to 7 carbon atoms, those having a hydroxyalkyl group of 1 to 4 carbon atoms or an imino group or can be dimerized by a spiro carbon atom, means. 2. Photosensitive material according to claim 1, characterized in that the haloalkane has the formula E-CX ₅ (I) wherein X is a halogen atom, "wherein the E radicals X from each other can be different or a hydrogen atom, However, not all Eeste X can consist of hydrogen atoms, and E can be a hydrogen atom Halogen atom, an alkyl group having 1 to 7 carbon atoms, a halogen-substituted alkyl group having 1 to 7 carbon atoms, an acyl group or one with one Acyl group substituted with halogen atom or arylsulfony group substituted with halogen atom, a nitro group or mean an aryl group » 3. Photosensitive material according to claim 1 or 2, characterized in that it contains a photosensitive layer which is a photosensitive haloalkane represented by the following formula (I), a furfurylidene acetal compound of the following formulas (Ha) or (IIb) and a phenol compound of the following formulas (purple) or (HIb) contains: E-Ca ^ 5 \ I ) wherein each Eest X may be the same or different and is a halogen atom or a hydrogen atom _s 303851/1063 23267S3 however, not every radical X consists of a hydrogen atom and R represents a hydrogen atom, a halogen atom or a halogen-substituted alkyl group having 1 to 3 carbon atoms means, CH (Ha) wherein R ^, and R ^ one or two phenyl groups or one
or two aralkyl groups with 6 to 9 carbon atoms, the phenyl or aryl ring in the aralkyl group with a halogen atom or an alkoxy group with 1 to 3
Carbon atoms may be substituted or one or two ITurfuryl groups; . (1Ib) 309851/1083 232679 O "3 wherein E, an alkylene group having 2 to 7 carbon atoms, those having a hydroxyalkyl group of 1 to 4 carbon atoms or an imino group or can be dimerized by a spiro carbon atom, means (OH) (HIa) (OH) (nib) where η is an integer from 1 to 3 and E ^ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group with 1 to 12 carbon atoms, a formyl group, a sulfo group or an acyl group having 1 to 4 carbon atoms mean. 4. Light ^ sensitive.s material according to claim 1 _t to 3, characterized in that the haloalkane of carbon tetrabromide, iodoform, carbon tetraiodine, hexachloroethane, hexafluoroethane, 1,2-Di j ο dathan, bromotriyod- ' 309851/1063 2S2S793 methane or chlorodiodomethane. 5 · Photosensitive material according to claims Λ to 4, characterized in that the Furfurylidenacetal from Difurfuryliden-pentaerythritol, furfurylidene-2-ethyl-2-hydroxymethyl-1,3-propylene ether, i'urfuryliden-Difurfuryläther, i ^l urfuryliden-2-methyl-2-furfurylidenimino-1, J -propylene ether, furfurylidene-tetramethylethylene ether, furfurylidene-diphenethyl ether, furfurylidene dibenzyl ether, iFurf uryli den-dianisyl ether-furfurylidene-dibenzohydryiether - or furfurylidene bis-Cp-chlorobenzyl ether). 6. Photosensitive material according to claim J bis 5, characterized in that the phenolic compound from pyrogallol, methyl gallate, ethyl gallate, n-propyl gallate, Isoamyl gallate, lauryl gallate, stearyl gallate, bile acid, Phloroglucinol, 2,4,6-trihydroxytoluene, 2,4,6-trihydroxy brenz acetophenone, J-methoxyji-catechol, 2,3,4-dihydroxybenzoic acid, 2, r5-dihydroxybenzoic acid, 2,6-dihydroxy-3,5-di-tert-butybenzoic acid, 2,6-dihydroxybenzaldehyde, 4,5-dihydroxytoluene, resorcinol , 4-chlororesorcinol, 3> ^5-l) il ¹ 7droxytoluol, hydroquinone, p-Hydrö ^ benzenesulfonic acid, p- ^ bromophenol, 1,5-dihydroxynaphthalene, 1, J-dihydroxynaphthalene or 2,7-dihydroxynaphthalene-3-sulfonic acid is . 7 · Light-sensitive material according to claims Λ to 6, characterized in that the light-sensitive layer additionally contains a film-forming binder. 8. Photosensitive material according to claim 7 * thereby characterized in that the binder is made from nitrocellulose, benzyl cellulose, polycarbonate, polyvinyl acetate, cellulose acetate, Cellulose acetate butyrate, cellulose acetate phthalate, polyvinyl chloride, polystyrene, polyester, polymethylinethacrylate, Polyvinylpyrrolidone, polyvinylbutyral or poly- 'phenylene oxide. 309851/1063 9. Light-sensitive material according to claim 1 "bis 8, characterized in that the weight ratio of haloalkane to furfurylidene acetal is 0.1 "to J. 10. Photosensitive material according to claim 9? characterized in that the weight ratio is O _S 5 Ms 2 ". 11. Photosensitive material according to claim 3 "bis 10, characterized in that the weight ratio from phenolic compound to furfurylidene acetate is 5 "or less. 12. Photosensitive material according to claim 11, characterized in that the weight ratio 0.05 to 2 13. Process for the production of a printing plate, characterized in that an element with a photosensitive layer is exposed imagewise ₉ which contains a photosensitive haloalkane compound with a dissociation energy of less than about 75 Kcal / mol, a furfurylidene acetal compound corresponding to the formulas Ha or Hb and contains a phenolic compound corresponding to the formulas IHa or IHb on a support, is then heated uniformly and with a Lö-. solvent to remove the unexposed areas is treated: 0-ϊ ° Λ N) --JE 03851/1063 wherein L and R ₂ EJ ^ne or two Fhenylgruppen or one or two aralkyl groups having 6 to 9 carbon atoms wherein the phenyl or aryl ring may be substituted in the aralkyl group having a halogen atom or an alkoxy group having 1 to 3 carbon atoms, or one or two Mean furfuryl groups, CH Ό. R- Man wherein R ^ is an alkylene group having 2 to 7 carbon atoms, which have a hydroxy alkyl group with 1 to 4 · carbon atoms or an imino group or be dimerized by a spiro carbon atom can means: IHa (OH) IHb 309851/1063 where η is an integer from 1 "to 3 and E ^, a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 "to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 1 "to 12 carbon atoms, a formyl group, a SuIfo group, an amino group or an acyl group with 1 "to 4 carbon atoms mean 14-. Process according to Claim 1J _V, characterized in that a haloalkane of the formula E-GX-, (I) is used, in which X is a halogen atom, where the radicals X can differ from one another, or a hydrogen atom, although not all radicals X are hydrogen atoms, and E can be a hydrogen atom, a halogen atom, an alkyl group having 1 to 7 carbon atoms, a halogen-substituted alkyl group having 1 to 7 carbon atoms, an acyl group or an acyl group substituted with a halogen atom or an arylsulfonyl group substituted with a halogen atom, a ÜSTitro group or an aryl group mean <> 15. The method according to claim I3 or 14, characterized in that that in the photosensitive layer? a binder is still used « 16. The method according to claim 15? characterized, that the following parts by weight of the specified components are used for one part by weight of the haloalkane be: JFufurylidene acetal about 0.05 "to about 50, Phenolic compound about 0.05 "to about 100, binder about 0.03 to about 100. 309651/1063